WO2021020741A1 - Composition de résine thermoplastique et article moulé formé à partir de celle-ci - Google Patents

Composition de résine thermoplastique et article moulé formé à partir de celle-ci Download PDF

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WO2021020741A1
WO2021020741A1 PCT/KR2020/008464 KR2020008464W WO2021020741A1 WO 2021020741 A1 WO2021020741 A1 WO 2021020741A1 KR 2020008464 W KR2020008464 W KR 2020008464W WO 2021020741 A1 WO2021020741 A1 WO 2021020741A1
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thermoplastic resin
resin composition
weight
vinyl
based copolymer
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PCT/KR2020/008464
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English (en)
Korean (ko)
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이진성
정현택
권영철
오현지
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롯데케미칼 주식회사
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Priority to JP2021573511A priority Critical patent/JP2022542503A/ja
Priority to US17/617,399 priority patent/US20220259421A1/en
Publication of WO2021020741A1 publication Critical patent/WO2021020741A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C08F220/325—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals containing glycidyl radical, e.g. glycidyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L35/06—Copolymers with vinyl aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a thermoplastic resin composition and a molded article formed therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in impact resistance, flame retardancy, heat resistance, fluidity, and appearance properties, and a molded article formed therefrom.
  • ABS resin acrylonitrile-butadiene-styrene copolymer resin
  • thermoplastic resin composition excellent in impact resistance, flame retardancy, heat resistance, fluidity, and appearance properties without such problems.
  • the background technology of the present invention is disclosed in Korean Patent Application Publication No. 2007-0004726.
  • An object of the present invention is to provide a thermoplastic resin composition excellent in impact resistance, flame retardancy, heat resistance, fluidity, and appearance characteristics.
  • Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.
  • thermoplastic resin composition comprises about 100 parts by weight of a rubber-modified aromatic vinyl-based copolymer resin; About 5 to about 20 parts by weight of a vinyl-based copolymer containing an epoxy group; About 0.5 to about 5 parts by weight of maleic anhydride-aromatic vinyl-based copolymer; About 8 to about 40 parts by weight of glass fibers; And about 10 to about 40 parts by weight of a phosphorus-based flame retardant, wherein the weight ratio of the vinyl-based copolymer including the epoxy group and the maleic anhydride-aromatic vinyl-based copolymer is about 1: 0.05 to about 1: 0.5. To do.
  • the rubber-modified aromatic vinyl-based copolymer resin comprises about 10 to about 50% by weight of a rubber-modified vinyl-based graft copolymer; And about 50 to about 90% by weight of an aromatic vinyl-based copolymer resin.
  • the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
  • the vinyl-based copolymer containing an epoxy group may be a polymerization of (meth)acrylate containing an epoxy group, an aromatic vinyl-based monomer, and a monomer copolymerizable with the aromatic vinyl-based monomer.
  • the vinyl-based copolymer containing an epoxy group may include about 0.01 to about 10 mol% of (meth)acrylate containing an epoxy group.
  • the maleic anhydride-aromatic vinyl-based copolymer may be a polymer of about 5 to about 40% by weight of maleic anhydride and about 60 to about 95% by weight of an aromatic vinylic monomer.
  • the total amount of the vinyl-based copolymer containing the epoxy group and the maleic anhydride-aromatic vinyl-based copolymer and the weight ratio of the glass fiber may be about 1: 0.5 to about 1: 4. .
  • the total amount of the vinyl-based copolymer including the epoxy group and the maleic anhydride-aromatic vinyl-based copolymer and the weight ratio of the phosphorus-based flame retardant may be about 1:1 to about 1:2.5. .
  • the thermoplastic resin composition may have a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of about 4 to about 10 kgf ⁇ cm/cm.
  • thermoplastic resin composition may have a flame retardancy of V-2 or more of a 0.75 mm thick specimen measured according to UL-94 standards, and a flame retardance of a 2.5 mm thick specimen of V-2 or more. I can.
  • the thermoplastic resin composition may have a Vicat softening temperature of about 80 to about 100° C. measured under a 5 kg load and 50° C./hr condition according to ISO 306.
  • the thermoplastic resin composition has a melt-flow index (MI) of about 5 to about 15 g/measured at 200° C. and 5 kg load condition according to ASTM D1238. It could be 10 minutes.
  • MI melt-flow index
  • thermoplastic resin composition may have a glossiness of about 90 to about 95% measured at a 60° angle according to ASTM D523.
  • thermoplastic resin composition may satisfy all of the following formulas 1 to 3:
  • Iz is the notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256;
  • Tv is the Vicat softening temperature measured under 5 kg load and 50°C/hr conditions according to ISO 306;
  • MI is a melt flow index measured at 200°C and 5 kg load condition according to ASTM D1238.
  • Another aspect of the invention relates to a molded article.
  • the molded article is characterized in that it is formed from the thermoplastic resin composition according to any one of the above 1 to 14.
  • the present invention has the effect of the invention to provide a thermoplastic resin composition excellent in impact resistance, flame retardancy, heat resistance, fluidity, appearance characteristics, and the like, and a molded article formed therefrom.
  • thermoplastic resin composition includes (A) a rubber-modified aromatic vinyl-based copolymer resin; (B) a vinyl-based copolymer containing an epoxy group; (C) maleic anhydride-aromatic vinyl-based copolymer; (D) glass fibers; And (E) a phosphorus-based flame retardant.
  • the rubber-modified aromatic vinyl-based copolymer resin of the present invention may include (A1) a rubber-modified vinyl-based graft copolymer and (A2) an aromatic vinyl-based copolymer resin.
  • the rubber-modified vinyl-based graft copolymer according to an embodiment of the present invention may be obtained by graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a rubbery polymer.
  • the rubber-modified vinyl-based graft copolymer can be obtained by graft polymerization of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer in a rubbery polymer.
  • the monomer mixture has processability and Graft polymerization can be performed by further including a monomer imparting heat resistance.
  • the polymerization can be performed by a known polymerization method such as emulsion polymerization and suspension polymerization.
  • the rubber-modified vinyl-based graft copolymer may form a core (rubber polymer)-shell (copolymer of a monomer mixture) structure, but is not limited thereto.
  • the rubber polymer includes a diene-based rubber such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene), and a saturated rubber hydrogenated to the diene-based rubber, isoprene rubber, and 2 to carbon atoms.
  • a diene-based rubber such as polybutadiene, poly(styrene-butadiene), and poly(acrylonitrile-butadiene
  • a saturated rubber hydrogenated to the diene-based rubber isoprene rubber, and 2 to carbon atoms.
  • 10 alkyl (meth)acrylate rubber, a copolymer of alkyl (meth)acrylate and styrene having 2 to 10 carbon atoms, ethylene-propylene-diene monomer terpolymer (EPDM), and the like can be exemplified. These may be applied alone or in combination of two or more.
  • the rubbery polymer may have an average particle size of about 0.05 to about 6 ⁇ m, for example about 0.15 to about 4 ⁇ m, specifically about 0.25 to about 3.5 ⁇ m.
  • the thermoplastic resin composition may have excellent impact resistance and appearance properties.
  • the average particle size (z-average) of the rubbery polymer (rubber particle) can be measured using a light scattering method in a latex state.
  • the rubbery polymer latex is filtered through a mesh to remove coagulation generated during the rubbery polymer polymerization, poured a solution of 0.5 g of latex and 30 ml of distilled water into a 1,000 ml flask, and filled with distilled water to prepare a sample. , 10 ml of a sample is transferred to a quartz cell, and the average particle size of the rubbery polymer can be measured with a light scattering particle size meter (malvern, nano-zs).
  • the content of the rubbery polymer may be about 20 to about 70% by weight, for example, about 25 to about 60% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer, and the monomer mixture (aromatic The content of the vinyl-based monomer and the vinyl cyanide-based monomer) may be about 30 to about 80% by weight, for example, about 40 to about 75% by weight of the total 100% by weight of the rubber-modified vinyl-based graft copolymer.
  • the thermoplastic resin composition may have excellent impact resistance and appearance properties.
  • the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinyl naphthalene, etc. can be illustrated. These can be used alone or in combination of two or more.
  • the content of the aromatic vinyl-based monomer may be about 10 to about 90% by weight, for example, about 40 to about 90% by weight of 100% by weight of the monomer mixture. In the above range, the processability and impact resistance of the thermoplastic resin composition may be excellent.
  • the vinyl cyanide monomer is copolymerizable with the aromatic vinyl, and includes acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, etc. Can be illustrated. These can be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used.
  • the content of the vinyl cyanide-based monomer may be about 10 to about 90% by weight, for example, about 10 to about 60% by weight of 100% by weight of the monomer mixture.
  • the thermoplastic resin composition may have excellent chemical resistance and mechanical properties.
  • the monomer for imparting processability and heat resistance may include (meth)acrylic acid, maleic anhydride, N-substituted maleimide, and the like, but is not limited thereto.
  • the content may be about 15% by weight or less, for example, about 0.1 to about 10% by weight of 100% by weight of the monomer mixture. In the above range, it is possible to impart processability and heat resistance to the thermoplastic resin composition without deteriorating other physical properties.
  • the rubber-modified vinyl-based graft copolymer is a copolymer (g-ABS) in which an aromatic vinyl-based styrene monomer and an acrylonitrile monomer, a vinyl cyanide-based compound are grafted onto a butadiene-based rubbery polymer, butyl acrylic
  • g-ASA acrylate-styrene-acrylonitrile graft copolymer
  • the rubber-modified vinyl-based graft copolymer (A1) is about 10 to about 50% by weight, for example, about 15 to about 45% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin (A). It can be included in %. Within the above range, the thermoplastic resin composition may have excellent impact resistance and molding processability.
  • the aromatic vinyl-based copolymer resin according to an embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a conventional rubber-modified aromatic vinyl-based copolymer resin.
  • the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture including an aromatic vinyl-based monomer and a vinyl cyanide-based monomer.
  • the aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer, a vinyl cyanide-based monomer, etc., and then polymerizing it, and the polymerization is known polymerization such as emulsion polymerization, suspension polymerization, bulk polymerization, etc. It can be done by a method.
  • the aromatic vinyl-based monomer is styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinyl naphthalene, etc. can be used. These may be applied alone or in combination of two or more.
  • the content of the aromatic vinyl-based monomer may be about 20 to about 90% by weight, for example, about 30 to about 80% by weight of the total 100% by weight of the aromatic vinyl-based copolymer resin.
  • the thermoplastic resin composition may have excellent impact resistance, fluidity, and appearance characteristics.
  • examples of the vinyl cyanide monomer may include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, and the like. These can be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile, etc. can be used.
  • the content of the vinyl cyanide monomer may be from about 10 to about 80% by weight, for example, from about 20 to about 70% by weight, based on 100% by weight of the total aromatic vinyl copolymer resin.
  • the thermoplastic resin composition may have excellent impact resistance, fluidity, heat resistance, and appearance.
  • the aromatic vinyl-based copolymer resin may be polymerized by further including a monomer for imparting processability and heat resistance to the monomer mixture.
  • a monomer for imparting the processability and heat resistance (meth)acrylic acid, N-substituted maleimide, and the like may be exemplified, but are not limited thereto.
  • the content may be about 15% by weight or less, for example, about 0.1 to about 10% by weight of 100% by weight of the monomer mixture. In the above range, it is possible to impart processability and heat resistance to the thermoplastic resin composition without deteriorating other physical properties.
  • the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 300,000 g/mol, for example, about 15,000 to about 150,000 g/mol. I can. Within the above range, the thermoplastic resin composition may have excellent mechanical strength and molding processability.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the aromatic vinyl-based copolymer resin (A2) is about 50 to about 90% by weight, for example, about 55 to about 85% by weight of 100% by weight of the total rubber-modified aromatic vinyl-based copolymer resin (A). Can be included. Within the above range, the thermoplastic resin composition may have excellent impact resistance, molding processability, and appearance characteristics.
  • the vinyl-based copolymer containing an epoxy group according to an embodiment of the present invention is applied together with a maleic anhydride-aromatic vinyl-based copolymer to improve miscibility between components of the thermoplastic resin composition, and thus included in the resin composition. It is possible to maximize the effect of improving the properties of each component.
  • the vinyl-based copolymer containing an epoxy group is a resin prepared so that an unsaturated epoxy group exists in the vinyl-based polymer, and can be prepared by polymerizing a monomer mixture consisting of an unsaturated epoxy-based compound containing an epoxy group and a vinyl-based compound have.
  • the polymerization may be performed by a known polymerization method such as emulsion polymerization, suspension polymerization, and bulk polymerization.
  • the unsaturated epoxy-based compound containing an epoxy group may be a (meth)acrylate containing an epoxy group such as glycidyl methacrylate and glycidyl acrylate. These may be applied alone or in combination of two or more.
  • the content of the unsaturated epoxy-based compound containing an epoxy group is about 0.01 to about 10 mol%, for example, about 0.05 to about 5 mol%, specifically about 0.1 to about 100 mol% of the vinyl-based copolymer containing an epoxy group. It may be 2 mol%. Within the above range, compatibility between each component of the thermoplastic resin composition may be excellent, and heat resistance and impact resistance may be excellent.
  • the vinyl-based compound may include an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer.
  • the content of the vinyl-based compound may be about 90 to about 99.99 mol%, for example, about 95 to about 99.95 mol%, and specifically about 98 to about 99.9 mol%, based on 100 mol% of the total vinyl-based copolymer containing an epoxy group. have. Within the above range, compatibility between each component of the thermoplastic resin composition may be excellent, and fluidity and impact resistance may be excellent.
  • the aromatic vinyl-based monomer is styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinyl naphthalene, etc. may be used, but the present invention is not limited thereto. These may be applied alone or in combination of two or more.
  • the content of the aromatic vinyl-based monomer may be about 40 to about 95% by weight, for example, about 40 to about 90% by weight of the total 100% by weight of the vinyl-based compound.
  • the monomer copolymerizable with the aromatic vinyl-based monomer is, for example, acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, ⁇ -chloroacrylonitrile, fumaronitrile, etc.
  • a vinyl cyanide compound or the like may be used, and may be used alone or in combination of two or more.
  • the content of the monomer copolymerizable with the aromatic vinyl-based monomer may be about 5 to about 60% by weight, for example, about 10 to about 60% by weight, based on 100% by weight of the total vinyl-based compound.
  • the vinyl-based copolymer containing an epoxy group has a weight average molecular weight (Mw) of about 50,000 to about 200,000 g/mol, for example, about 100,000 to about 150,000 g/mol, as measured by gel permeation chromatography (GPC).
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the content of the vinyl-based copolymer containing an epoxy group is about 5 to about 20 parts by weight, for example, about 10 to about 18 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.
  • the content of the vinyl-based copolymer containing the epoxy group is less than about 5 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, the appearance characteristics, flame retardancy, impact resistance, etc. of the thermoplastic resin composition may be reduced. There is a concern, and if it exceeds about 20 parts by weight, there is a concern that the fluidity, impact resistance, and the like of the thermoplastic resin composition are deteriorated.
  • the maleic anhydride-aromatic vinyl-based copolymer according to an embodiment of the present invention is applied together with the vinyl-based copolymer containing the epoxy group to improve miscibility between the components of the thermoplastic resin composition, and each contained in the resin composition It is a polymer of maleic anhydride and an aromatic vinyl monomer that can maximize the effect of improving the properties of the component.
  • the maleic anhydride-aromatic vinyl-based copolymer may be obtained by mixing maleic anhydride and an aromatic vinyl-based monomer, and then polymerizing them, and the polymerization is known as emulsion polymerization, suspension polymerization, bulk polymerization, etc. It can be carried out by the polymerization method of.
  • the aromatic vinyl-based monomer is styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, dibromostyrene , Vinyl naphthalene, etc. can be used. These may be applied alone or in combination of two or more.
  • the maleic anhydride may be included in an amount of about 5 to about 40% by weight, for example, about 10 to about 35% by weight, based on 100% by weight of the total maleic anhydride-aromatic vinyl-based copolymer, and the aromatic vinyl-based
  • the monomer may be included in about 60 to about 95% by weight, for example about 65 to about 90% by weight, based on 100% by weight of the total maleic anhydride-aromatic vinyl-based copolymer.
  • the thermoplastic resin composition may have excellent heat resistance and impact resistance.
  • the maleic anhydride-aromatic vinyl-based copolymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 50,000 to about 150,000 g/mol, for example, about 60,000 to about 120,000 g/ may be mol.
  • Mw weight average molecular weight measured by gel permeation chromatography
  • the thermoplastic resin composition may have excellent impact resistance and fluidity.
  • the maleic anhydride-aromatic vinyl-based copolymer is included in about 0.5 to about 5 parts by weight, for example, about 1 to about 4.5 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.
  • the content of the maleic anhydride-aromatic vinyl-based copolymer is less than about 0.5 parts by weight based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, the appearance properties, heat resistance, impact resistance, etc. of the thermoplastic resin composition are lowered. If it exceeds about 5 parts by weight, there is a fear that the fluidity, appearance properties, etc. of the thermoplastic resin composition may decrease.
  • the weight ratio (B:C) of the vinyl-based copolymer (B) containing the epoxy group and the maleic anhydride-aromatic vinyl-based copolymer (C) is about 1: 0.05 to about 1: 0.5, for example, it may be about 1: 0.07 to about 1: 0.4, and specifically about 1: 0.1 to about 1: 0.3.
  • the weight ratio of the vinyl-based copolymer containing the epoxy group and the maleic anhydride-aromatic vinyl-based copolymer is less than about 1: 0.05, there is a concern that the appearance characteristics, impact resistance, etc. of the thermoplastic resin composition may be deteriorated, and about 1: When it exceeds 0.5, there is a concern that the fluidity, flame retardancy, and the like of the thermoplastic resin composition are deteriorated.
  • the glass fiber according to an embodiment of the present invention is capable of improving the stiffness and heat resistance of the thermoplastic resin composition, and a glass fiber used in a conventional thermoplastic resin composition may be used.
  • the glass fibers may be in the form of fibers, and may have cross-sections of various shapes such as round, oval, and rectangular. For example, it may be desirable in terms of mechanical properties to use fibrous glass fibers of circular and/or rectangular cross section.
  • the circular cross-section of the glass fiber may have a cross-sectional diameter of about 5 to about 20 ⁇ m and a length before processing of about 2 to about 20 mm
  • the rectangular cross-section of the glass fiber has an aspect ratio of the cross-section (long diameter of the cross-section/ The short diameter of the cross section) may be about 1.5 to about 10, the short diameter may be about 2 to about 10 ⁇ m, and the length before processing may be about 2 to about 20 mm.
  • the stiffness and heat resistance of the thermoplastic resin composition may be improved.
  • the glass fibers may not be treated with a surface treatment agent.
  • the glass fiber may be included in an amount of about 8 to about 40 parts by weight, for example, about 10 to about 35 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.
  • the content of the glass fiber is less than about 8 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a concern that the stiffness, heat resistance, etc. of the thermoplastic resin composition may decrease, and exceed about 40 parts by weight. In this case, there is a concern that the appearance characteristics, impact resistance, and the like of the thermoplastic resin composition may be deteriorated.
  • the total amount of the vinyl-based copolymer (B) and the maleic anhydride-aromatic vinyl-based copolymer (C) containing an epoxy group and the weight ratio (B+C:D) of the glass fiber (D) is about 1 : 0.5 to about 1: 4, for example, it may be about 1: 0.9 to about 1: 3.
  • the thermoplastic resin composition may have excellent impact resistance, fluidity, heat resistance, and appearance characteristics.
  • the phosphorus-based flame retardant according to an embodiment of the present invention may be a phosphorus-based flame retardant used in a conventional flame-retardant thermoplastic resin composition.
  • Phosphorus-based flame retardants can be used.
  • the phosphorus-based flame retardant may include an aromatic phosphate-based compound represented by the following formula (1).
  • R 1 , R 2 , R 4 and R 5 are each independently a hydrogen atom, a C6-C20 aryl group or a C6-C20 aryl substituted with a C1-C10 alkyl group
  • R 3 is a C6-C20 arylene group or a C6-C20 arylene group substituted with a C1-C10 alkyl group, for example, a dialcohol such as resorcinol, hydroquinone, bisphenol-A, bisphenol-S, And n is an integer from 0 to 10, for example 0 to 4.
  • aromatic phosphate ester compound represented by Formula 1 when n is 0, diaryl phosphate such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trizyrenyl phosphate, tri(2,6-dimethyl) Phenyl) phosphate, tri(2,4,6-trimethylphenyl) phosphate, tri(2,4-diteributylphenyl) phosphate, tri(2,6-dimethylphenyl) phosphate, etc.
  • diaryl phosphate such as diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, trizyrenyl phosphate, tri(2,6-dimethyl) Phenyl) phosphate, tri(2,4,6-trimethylphenyl) phosphate, tri(2,4-diteributylphenyl) phosphate, tri(2,6-dimethylphenyl) phosphate, etc.
  • n 1
  • bisphenol-A bis (diphenyl phosphate), resorcinol bis (diphenyl phosphate), resorcinol bis [bis (2,6-dimethylphenyl) phosphate], resorcinol bis [bis (2,4 -Ditertiary butylphenyl) phosphate], hydroquinone bis [bis (2,6-dimethylphenyl) phosphate], hydroquinone bis [bis (2,4-ditertiary butyl phenyl) phosphate] and the like can be exemplified. Not limited. These may be applied alone or in the form of a mixture of two or more.
  • the phosphorus-based flame retardant may be included in an amount of about 10 to about 40 parts by weight, for example, about 15 to about 35 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.
  • the content of the phosphorus-based flame retardant is less than about 10 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin, there is a concern that the flame retardancy, fluidity, etc. of the thermoplastic resin composition may decrease, and exceed about 40 parts by weight. In this case, there is a concern that the heat resistance, impact resistance, etc. of the thermoplastic resin composition may be deteriorated.
  • the weight ratio (B+C:E) of the total amount of the vinyl-based copolymer (B) and the maleic anhydride-aromatic vinyl-based copolymer (C) including the epoxy group and the phosphorus-based flame retardant (E) is about 1 : 1 to about 1: 2.5, for example, it may be about 1: 1.3 to about 1: 2.
  • the thermoplastic resin composition may have excellent flame retardancy, heat resistance, appearance characteristics, and fluidity.
  • the thermoplastic resin composition according to an embodiment of the present invention may further include additives included in a conventional thermoplastic resin composition.
  • the additive include, but are not limited to, anti-drip agents such as fluorinated olefin resins, antioxidants, lubricants, release agents, nucleating agents, stabilizers, pigments, dyes, mixtures thereof, and the like.
  • the content may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, based on about 100 parts by weight of the rubber-modified aromatic vinyl-based copolymer resin.
  • thermoplastic resin composition according to an embodiment of the present invention is in the form of pellets obtained by mixing the constituents and melt-extruding at about 200 to about 280°C, for example, about 220 to about 260°C using a conventional twin screw extruder. I can.
  • the thermoplastic resin composition has a notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256 of about 4 to about 10 kgf ⁇ cm/cm, for example about 4.5 to about 9 kgf ⁇ cm May be /cm.
  • the thermoplastic resin composition may have a flame retardancy of V-2 or more, respectively, of a 0.75 mm thick specimen and a 2.5 mm thick specimen measured according to UL-94 standards.
  • the thermoplastic resin composition may have a Vicat softening temperature of about 80 to about 100°C, for example, about 81 to about 90°C, measured under a 5 kg load and 50°C/hr condition according to ISO 306. .
  • the thermoplastic resin composition has a melt-flow index (MI) of about 5 to about 15 g/10 minutes, as measured at 200° C. and 5 kg load condition, according to ASTM D1238, for example It may be about 6 to about 15 g/10 minutes, specifically about 7 to about 10 g/10 minutes.
  • MI melt-flow index
  • the thermoplastic resin composition may have a gloss measured at a 60° angle of about 90 to about 95%, for example, about 91 to about 94% according to ASTM D523.
  • thermoplastic resin composition may satisfy all of the following formulas 1 to 3.
  • Iz is the notched Izod impact strength of a 1/8" thick specimen measured according to ASTM D256;
  • Tv is the Vicat softening temperature measured under 5 kg load and 50°C/hr conditions according to ISO 306;
  • MI is a melt flow index measured at 200°C and 5 kg load condition according to ASTM D1238.
  • the molded article according to the present invention is formed from the thermoplastic resin composition.
  • the thermoplastic resin composition may be manufactured in the form of pellets, and the manufactured pellets may be manufactured into various molded articles (products) through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such a molding method is well known by those of ordinary skill in the field to which the present invention belongs. Since the molded article is excellent in impact resistance, flame retardancy, heat resistance, fluidity, and appearance characteristics, it is useful as an exterior material for construction.
  • G-ABS in which 55% by weight of styrene and acrylonitrile (weight ratio: 75/25) was graft-copolymerized to a butadiene rubber having a Z-average of 310 nm of 45 % by weight was used.
  • a SAN resin (weight average molecular weight: 130,000 g/mol) in which 75% by weight of styrene and 25% by weight of acrylonitrile were polymerized was used.
  • a PMI-SAN resin (weight average molecular weight: 130,000 g/mol) in which 20% by weight of N-phenylmaleimide, 65% by weight of styrene, and 15% by weight of acrylonitrile were polymerized was used.
  • Styrene-maleic anhydride copolymer (SMA resin, weight average molecular weight: 80,000 g/mol, styrene/maleic anhydride (weight ratio): 74/26) was used.
  • Bisphenol-A diphosphate (manufacturer: Yoke Chemical, product name: YOKE BDP) was used.
  • Notched Izod (IZOD) Impact Strength (Unit: kgf ⁇ cm/cm): Based on the evaluation method specified in ASTM D256, the notched Izod impact strength of a 1/8" thick specimen was measured.
  • VST Vicat Softening Temperature
  • MI Melt-flow Index
  • Glossiness (gloss, unit: %): Using Suga's UGV-6P Gloss Meter, measure the glossiness of a 90 mm ⁇ 50 mm ⁇ 2 mm size specimen at a 60° angle according to the evaluation method specified in ASTM D523. Measured.
  • Example One 2 3 4 5 6 7 (A) (parts by weight) 100 100 100 100 100 100 100 100 100 100 100 (B1) (parts by weight) 14 14 14 10 20 10 10 (B2) (parts by weight) - - - - - - - (C) (parts by weight) 1.4 2.8 4.2 2.8 2.8 0.5 5 (D) (parts by weight) 20 20 20 20 20 20 20 (E) (parts by weight) 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20
  • thermoplastic resin compositions (Examples 1 to 7) of the present invention are excellent in impact resistance, flame retardancy, heat resistance, fluidity, and appearance characteristics.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention porte sur une composition de résine thermoplastique comprenant : environ 100 parties en poids d'une résine de copolymère à base de vinyle aromatique modifiée par du caoutchouc ; environ 5 à environ 20 parties en poids d'un copolymère à base de vinyle contenant un groupe époxy ; environ 0,5 à environ 5 parties en poids d'un copolymère à base de vinyle aromatique anhydride maléique ; environ 8 à environ 40 parties en poids de fibres de verre ; et environ 10 à environ 40 parties en poids d'un agent ignifuge à base de phosphore, le rapport en poids du copolymère à base de vinyle contenant un groupe époxy et du copolymère à base de vinyle aromatique anhydride maléique étant d'environ 1:0,05 à environ 1:0,5. La composition de résine thermoplastique est excellente en termes de résistance aux chocs, d'ininflammabilité, de résistance à la chaleur, de fluidité, de caractéristiques d'aspect, etc.
PCT/KR2020/008464 2019-07-30 2020-06-29 Composition de résine thermoplastique et article moulé formé à partir de celle-ci WO2021020741A1 (fr)

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US17/617,399 US20220259421A1 (en) 2019-07-30 2020-06-29 Thermoplastic Resin Composition and Molded Article Formed Therefrom

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US20230033321A1 (en) * 2021-08-02 2023-02-02 B/E Aerospace, Inc. Fire resistant thermoplastic-based resin for fiber-reinforced composites
FR3140885A1 (fr) * 2022-10-18 2024-04-19 Skytech Compositions de polymères styréniques de grade extrusion

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20230046439A (ko) * 2021-09-30 2023-04-06 롯데케미칼 주식회사 열가소성 수지 조성물 및 이로부터 제조된 성형품

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JPH0753833A (ja) * 1993-08-18 1995-02-28 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
KR20030030420A (ko) * 2001-10-11 2003-04-18 제일모직주식회사 열가소성 수지조성물
KR20060079106A (ko) * 2004-12-31 2006-07-05 주식회사 엘지화학 열융착성, 내화학성, 충격강도, 신율, 및 도장 퍼짐성이우수한 초내열 열가소성 수지 조성물
KR101486565B1 (ko) * 2011-12-05 2015-01-26 제일모직 주식회사 열가소성 수지 조성물 및 이를 이용한 성형품
KR20170036842A (ko) * 2015-09-18 2017-04-03 롯데첨단소재(주) 난연성 열가소성 수지 조성물 및 이로부터 형성된 성형품

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JPH0753833A (ja) * 1993-08-18 1995-02-28 Japan Synthetic Rubber Co Ltd 熱可塑性樹脂組成物
KR20030030420A (ko) * 2001-10-11 2003-04-18 제일모직주식회사 열가소성 수지조성물
KR20060079106A (ko) * 2004-12-31 2006-07-05 주식회사 엘지화학 열융착성, 내화학성, 충격강도, 신율, 및 도장 퍼짐성이우수한 초내열 열가소성 수지 조성물
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KR20170036842A (ko) * 2015-09-18 2017-04-03 롯데첨단소재(주) 난연성 열가소성 수지 조성물 및 이로부터 형성된 성형품

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Publication number Priority date Publication date Assignee Title
US20230033321A1 (en) * 2021-08-02 2023-02-02 B/E Aerospace, Inc. Fire resistant thermoplastic-based resin for fiber-reinforced composites
US11879042B2 (en) * 2021-08-02 2024-01-23 B/E Aerospace, Inc. Fire resistant thermoplastic-based resin for fiber-reinforced composites
FR3140885A1 (fr) * 2022-10-18 2024-04-19 Skytech Compositions de polymères styréniques de grade extrusion

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